Mordant azo dyestuffs and a process for making same



P to each other.

Patentecl Apr. 11, 1939 UNITED STATES PATENT OFFICE MORDANT AZO DYESTUFFS AND A PROCESS FOR MAKING SAME No Drawing. Application May 19, 1937, Serial No. 143,624. In Germany May 28, 1936 24 Claims.

' This invention relates to the manufacture of valuable mordant dyeing disazoor polyazo-dyestuffs by coupling 2-amino-5-oxynaphthalene-'7- sulphonicacid twice toproduce a compound corresponding with the formula liiazo-compoundl ll) f Diazo-compound II the first coupling being in an acid medium and the second in an alkaline medium. Of the two diam-compounds I and II indicated in the formula at least one must be derived from an orthoaminophenol or ortho-aminonaphthol and at least one must contain the usual mordant groups such as hydroxyl and carboxyl in ortho-position These two requirements may be united in the same diazo-compound, for example the'latter may be diazotized ortho-amino-salicylic acid. The new dyestuffs are of particular valuein the form oftheir complex metal compounds, into which they may be converted by treatment with suitable agents yielding metal in the manner now well known. Thus for example, by the process described in British Specification No. 26460/1912, new dyestuffs may be obtained which retain the original solubility in water but contain chromium and still have the character of chrome mordant dyestuifs. According to the proportion of the chroub mium compound used in the production or according to the conditions of reaction the proportion of the chromium combined in the dyestuif may vary within certain limits, either all the groups present capable of being chromed or only 0 apart thereof being saturated with chromium. Instead of chromium other trivalent metals, for in'stanceiron, may be introduced.

If, instead of trivalent compounds, bivalent metal compounds are usedin the treatment, there are produced complex metalliferous dyestuffs which are also soluble in water and have inpart quite different tints from those of the parent dyestufis. They also have the character of mordant dyestuffs and constitute a valuable addition'to dyestuffs of this class. The new dyestuffs may contain difi'erent metals simultaneously, for example a compound into which-a bivalent metal has already been intro- 55 duced may be converted by treatment with a compound of a trivalent metal into water-soluble compounds which contain both the biand tri-valent metals in union.

All these metal compounds are suitable for all the usual methods of dyeing and printing mor- 5 dant dyestufis on various fibres, for instance cotton, artificial silk: from regenerated cellulose, natural silk; in general the tints obtained are faster than those obtainable in analogous manner with the corresponding dyestuifs which have not been treated with metal.

In particular these metal compounds may be printed on the fibre in suitable manner with chromium mordants, for instance by the processes described in British Specification Nos. 15, 26460/1912 and. 319457, U. S. Patent No. 1,848,598,

U. S. patent application Serial No. '716,001, whereby, even after a short steaming, prints are obtained of excellent fastness.

The invention is illustrated by the following examples, the parts being by weight:

Example 1 15.3 parts of para-aminosalicylic acid are diazotized in the usual manner and coupled in acetic acid solution with 23.9 parts of Z-amino- 5-hydr0xynaphthalene-7-sulphonic acid. When the acid coupling is complete, the product is further coupled in alkaline solution with the diazo-solution from 23.4 parts of l-amino-Z-hydroxy-3-nitrobenzene-5-sulphonic acid. When this coupling is complete, the dyestuff is salted out. It dissolves in water to a violet solution which changes towards red on addition of dilute acids, becoming of lighter colour. When printed on cotton followed by a short steaming the dyestuff yields a deep-grey which on prolonged steaming becomes greenish.

When the solution of the dyestufi is heated for a long time with a substance that yields chromium, for instance chromium acetate, there is obtained a complex chromium compound which may be obtained in solid form by evaporating the solution. The solution of this compound in water is blue-grey and no longer suffers change of colour on addition of acids. The new chromium compound yields when printed on cotton followed by short or long steaming a deep greenish-grey which is characterized by good fastness to soaping, washing and light.

By prolonged heating with chromium lactate a chromium compound is obtained which can be dyed in an acid bath on natural silk in union with a suitable chromium mordant; neutral grey tints are obtained which are not varied on soaping.

If in the alkaline coupling there is used instead of the diazo-compound of 1-amino-2-hydr-oxy-3-nitrobenzene-5-sulphonic acid the diazocompound of another ortho-aminophenol, for instance l-amino-Z-hydroxy-3-nitro-5-chlorobenzene or picramic acid, similar dyestufis are obtained which also yield grey to black tints when chrome printed on cotton.

Example 2 23.3 parts of para-amino-ortho-sulpho-salicylic acid are diazotized in the usual manner and coupled in acetic acid solution with 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulphonicacid. The mono-azo-dyestufi' thus obtained is coupled in alkaline solution with the diazo-compound of 23.4 parts of 1-amino-2-hydroxy-3-nitrobenzene-5-sulphonic acid and on completion of the coupling the new diazo-dyestuff is salted out. It dissolves in water to a red-violet solution; on adding acid to the solution the colour becomes lighter and changes towards bright-red. When printed on cotton with chromium acetate the new dyestufi yields after a short steaming a violetishgrey and on a longer steaming a somewhat greenish-grey.

By boiling the solution of the dyestufi" with an agent yielding chromium, for example chromium acetate, there is obtained a complex chromium compound of the dyestufi which dissolves in water to a blueblack solution that does not suffer change of colour on addition of acid. This new chromium compound yields on cotton printing followed by short or long steaming a neutral grey-black of good fastness to soaping, washing and light.

On boiling the dyestuff with a solution of chromium lactate there is produced a chromium compound which is not suitable in this form for dyeing silk, since it separates in flocks in the dye bath. If the compound is boiled with caustic soda lye and salted out after neutralizing the lye, there is obtained a chromium compound which dyessilk in an acid bath in presence of a suitable chromium mordant. Grey-green tints are obtained which are not changed by sc aping.

and are characterized by their good fastness to washing and to perspiration.

Example 3 grey of good fastness to soap and washing and of rather good fastness to chlorine.

Example 4 15.3 parts of ortho-aminosalicyclic acid are diazotized as usual and coupled in an acetic acid solution with 23.9 parts of 2-amino-5-hydroxynaphthalene-'l-sulphonic acid. The mono-azodyestufi thus obtained is coupled in alkaline solution with the diazo-compound of 23.4 parts of 1-amino-2-hydroxy-3-nitrobenzene-5-sulphonic acid and when coupling is complete the dyestuff is salted out. It dissolves in water to a blue-red solution, changed towards violet by the addition of caustic soda lye and becoming lighter and changing towards yellow-red on the addition of acids. When chrome printed on cotton the colour is a muddy violetish-grey of poor fastness to soap, washing and chlorine after a short steaming and a greenish-grey after a longer steaming.

The chromium compound obtained in the usual manner by boiling with an agent that yields chromium dissolves in water to a grey-blue colour which is not changed either by alkali or by acid. In cotton printing the new chromium compound yields a grey-blue tint of good properties of fastness, whether the steaming be long or short.

Example 5 23.3 parts of ortho-amino-para-sulpho-salicylic acid are diazotized as usual and the diazocompound is coupled in acetic acid solution with 23.9 parts of 2-amino-5-hydroxy-naphthalene-7- sulphonic acid. The mono-azo-dyestuff thus obtained is coupled in alkaline solution with the diazo-compound from 22.1 parts of sodium picramate and the disazo-dyestun" is saltedout when the coupling is complete. This new dyestuff dissolves in water to a bluish-red solution; on addition of acid the solution becomes lighter in colour with a change towards bright red. The dyestufi is somewhat sparingly soluble in water and yields with chromium acetate on cotton prints which are muddy blue-violet after a short steaming and violetish-black after a longer steaming; the fastness to chlorine is poor, but to washing moderately good; there is considerable loss of colour on boiling with soap.

If the solution of the dyestufi is heated with a substance that yields chromium, for instance chromium acetate, for a long time, there is obtained a chromium compound which dissolves in water to a grey-blue solution. This colour is not changed either by alkali or by acid. When printed on cotton the new chromium compound yields a greenish-grey both on short steaming and long steaming, which has good fastness to soaping, washing and chlorine and a very good fastness to light.

If a solution of chromium sulphate is used as the chroming agent there is obtained a sparingly soluble compound which dissolves when boiled with sodium carbonate to a grey-blue solution. This compound can be salted out from the solution. It has properties similar to those of the product made with the aid of chromium acetate and is also suitable for printing on cotton.

Example 6 The mono-azo-dyestuff obtainable as described in Example 5 is coupled in alkaline solution with the diazo-compound from 23.3 parts of orthoamino-para-sulpho-salicyclic acid. This new dyestufi dissolves in water to a red solution which becomes more blue and of deeper. colour on addition of alkali. By printing on cotton with a chrome mordant muddy violet tints are obtained, Whether the steaming be short or long, which are of poor fastness to chlorine and washing.

By treatment with an agent yielding chromium there is produced a complex chromium compound of the dyestuff which dissolves in Water to a steelblue solution which remains unchanged on addition of alkali or acid. In printing on cotton the chromium compound yields a neutral grey or good properties of fastness.

Example 7 The mono-azo-dyestufi obtainable as described in Example 5 is coupled in alkaline solution with the diazo-compound from 23.4 parts of l-amino-2-hydr0xy- 3 -nitrobenzene-5-sulphonic acid. This new disazo-dyestufi dissolves in water to a violet solution which becomes more blue on addition of alkali; with acids the colour becomes lighter and changes towards yellow-red. Chrome printing of the dyestuff produces muddy violetish-grey tints.

The chromium compound made in the usual manner dissolves in water to a steel-blue solution which does not change colour by addition of alkalior acid. When printed on cotton the compound yields grey-blue tints of good properties of fastness both on short and on longer steaming.

Example 8 The chromium compound obtained in the usual manner dissolves in water to a blue-grey solution. When printed. on cotton it. yields a neutral grey ofrgood properties of fastness.

Example 9 33.7 parts of 3-amino-4-sulphobenzene-azosalicylic acid are diazotized as described in U, S. Patent No. 2,024,797 and then coupled in acetic acid solution with 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulphonic acid. The disazodyestufi thus obtained is coupled in alkaline solution with the diazo-compound from 22.4 parts of 1 hydroxy 2 amino 4 chlorobenzene fi-sulphonic acid and when coupling is complete, the trisazo-dyestufi is salted out. It dissolves in water to a. violetish-brown solution. When chrome printed on cotton it yields a dark-brown.

Example 1 The disazo-dyestufi' made as described in Example 9 is coupled in alkaline solution with the diazo-compound from 23.3 parts of ortho-aminopara-sulpho-salicylic acid and when coupling is complete, the trisazo-dyestufi is salted out. The new dyestufi dissolves in water to a brown-red solution. When chrome printed on cotton it yields brown prints when the steaming is short and violetish-brown prints of poorer fastness to chlorine and washing when the steaming is long.

When treated with an agent yielding chromium the dyestufi yields a complex chromium compound which dissolves in water to a brown solution. When printed on cotton it yields a darkbrown of good properties of fastness.

When the dyestuff is treated with a copper salt, for instance by heating it with copper sulphate, there is obtained a complex copper compound which dissolves in water to a bluish-red solution. This compound yields when chrome printed on cotton or artificial silk from regenerated cellulose a reddish-brown. In like manner treatment with a nickel salt yields a complex nickel compound which when chrome printed on cotton yields a brown.

The non-metalliferous dyestufi dyes natural silk in an acid bath in presence of a suitable chromium mordant. The red-brown dyeing thus obtained may be subsequently treated on the fibre with a copper salt, whereby the fastness to light of the dyeing is essentially increased.

It is also possible in accordance with the invention to prepare a large number of other dyestuffs of which some are illustrated in the following table:

Colour of a solution of the Component coupled in g fif l gfi of the chromium compound of y Chromium the dyestufi m- Chrome print of the print of the h dyes/cuff c IOIIlllllIl Concentrated Concentrated compound Acid medium Alkaline medium Water sulphuric Water sulphuric acid acid Orthoaminosalicylic 1 -hydroxy -2 -amiuo-4-chlo- Violet Violet Grey-blue..- Bluish grey. Violet Bluish grey.

acid. rolaenzene-dsulphonic aci Do 1-hydroxy-2-amino-6-methdo .do Grey Greenish do Greenishyl-i-nitrobenzene. grey. grey. Do l-amino-2-hydroxy-5-chloro- Red-violet- Blue-violet" R e d d 1 s h Blue-greydo Blue-grey.

4-nitrobenzene. blue-grey. Do fi-nitro-z-aminophenol Violet Violet Grey-blue... .do Blue-violet" G r e e n i s h yo-Amino-p-sulphd i-hydroxy-2-amino-4-chlcrc Blue-violet Blue Blue-grey. .....do Violet Blue-grey.

salicylic acid. benzene-fi-sulphonic acid.

D0, l-hydroxy-Z-amino-i-nitro- Red-violet Blue-violet Yellowish- Greenish- Red-violet Grey.

fi-methylbenzene. grey. grey. 1-amino-2-hydroxy-3-nitro- Blue-violet Blue Blue-grey. do Violet G r e e n i s h fi-chlorobenzene. grey. 1-amino-2-hydroxy-4-nitro- Violet Grey-blue..- Grey "do Grey-violet Do.

fi-chlorobenzene. 5-nitro-2-aminophenol R e d d is h do G reen lSh- Grey-greem. .do Do.

blue. grey. l-hydroxy-2-amino-4-methdo Blue-vl0let Grey Grey-blue M u d d y Grey.

yl-fi-nitrobenzene. violet. Lhydroxy-Z-amino-lenitro- Red Dark-violet. Grey-blade- .do Darkviolet Greenisli benzene-fi-sulphonic acid. grey. o-Amino-p-chloro- Picraminic acid do Blue-violet M u (1 (1y do Violet Do.

salicylic acid. 7 1grgey v10- e l-hydr'oxy-Z-aminoo-Amino-p-sulphcsalicylic Red-violet" Brown-vio- Blue-grey--- Blue ..do Do.

6-nitrobenzene-4- acid. let. sulphonic acid. l-hydroxy-Z-aminodo do Red-violet Violet Blue-violet Blue-violet B l u i s h 'l-clilorobenzenegrey. fi-sulphonic acid.

Diem-compound II the two diam-compounds I and II being derived from an aromatic crtho-hydroxy-amine and at least one of them having a hydroxy group and a carboxyl group in ortho-position to one another,

and treating the dyestufi thus obtained with metal yielding agents.

2. A process of preparing mordant polyazodyestulis and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-'l-sulphonic acid twice, a first time in a weak acid medium with a diazo-compound I and a second time in an alkaline medium with a diazo-compound II, to produce a dyestuff or the general type:

1|)iazo-componnd I Diem-compound II- the two diam-compounds I and II being derived from an aromatic ortho-hydroXy-amine and both of them having a carboxyl group in ortho-position to a hydroxy group, and treating the dye stufi's thus obtained with metal yielding agents.

3. A process of preparing mordant polyazodyestuffs and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-'Z-sulphonic acid twice, a first time in a weak acid medium with a diazo-compound I and a second time in an alkaline medium with a diazo-compound II, to produce a dyestufi of the general type:

l')iazo-compcund I Blaze-compound II- the two diazo-compounds I and II being derived from an ortho-amino-phenol-compound and at least one of them having a hydroxy group and a carboxyl group in ortho-position to one another, and treating the dyestuff thus obtained with metal yielding agents.

4. A process of preparing mordant polyazodyestuffs and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-'l-sulphonic acid twice, a first time in a weak acid medium with a diazo-compound I and a second time in an alkaline medium with ll iazo-compound I Diem-compound II I OH the two diazo-compounds I and II being derived from an ortho-amino-phenol-compound and both of them having a carboxyl group in ortho-position to a hydroxy group, and treating the dyestufi thus obtained with metal yielding agents.

5. A process of preparing mordant polyazodyestufis and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-'I-sulphonic acid twice, a first time in a weak acid medium with a diazotized orthoamino-salicylic-acid-compound and a second time in an alkaline medium with a diazotized ortho-amino-phenol-compound, and treating the dyestuff thus obtained with metal yielding agents.

6. A process of preparing mordant polyazodyestufis and water soluble metal compounds thereof, comprising coup-ling 2-amino-5-hydroxynaphthalene-'l-sulphonic acid twice, a first time in a weak acid medium with diazotized orthoamino-para-sulphosalicylic acid and a second time in an alkaline medium with a diazotized ortho-amino-phenol-compound, and treating the dyestuii thus obtained with metal yielding agents.

7. A process of preparing mordant polyazodyestuii and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-7-sulphonic acid twice, a first time in a weak acid medium with a diazotized orthoamino-salioylic-acid-compound and a second time in an alkaline medium with a diazotized orthoamino-salicylic-acid-compound, and treating the dyestuii thus obtained with metal yielding agents.

8. A process of preparing mordant polyazodyestuffs and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-'Y-sulphonic acid twice, a first time in a weak acid medium with diazotized orthoamino-para-sulpho-salicylic acid and a second time in an alkaline medium with diazotized ortho amino para sulpho salicylic acid, and treating the dyestuff thus obtained with metal yielding agents.

9. A process of preparing mordant polyazodyestuffs and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-'7-sulphonic acid twice, a first time in a weak acid medium with a diazo-compound I and a second time in an alkaline medium with a diazo-compound II, to produce a dyestuff of the general type:

Iiiazo-compound I Diem-compound II- the two diazo-compounds I and II being derived from an aromatic ortho-hydroxy-amine and at least one of them having a hydroxy group and a carboxyl group in ortho-position to one another, and treating the dyestuff thus obtained with an agent yielding a bivalent metal.

10. A process of preparing mordant polyazodyestufis and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-Wsulphon'ic acid twice, a first time in a weak acid medium with a diazo-compound I and a second time in an alkaline medium with a; dlazo-compound II, to produce a :dyestufi of the general type: V

Diazo-compound I HSOa- NH:

Diazo-compoundll the two diazo-compounds I and II being derived from an aromatic ortho-hydroxy-amine and at least one of them having a hydroxy group and a carboxyl group in ortho-positio-n to one another, and treating the dyestuif thus obtained with a copper yielding agent.

11. A process of preparing mordant polyazodyestufis and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-7-sulphonic acid twice, a. first time in a weak acid medium with a diazo-compound I: and a second time in an alkaline medium with a diazo-compound II, to produce a dyestuff of the general type:

Diazo-compound I Diazo-compound II- the two diazo-compounds I and II being derived from an aromatic ortho-hydroxy-amine and at least one of them having a hydroxy group and a'carboxyl group in ortho-position to one another, and treating the dyestuff thus obtained with copper sulphate.

12, A process of preparing mordant poly-azodyestuffs and water soluble metal compounds thereof, comprising coupling Z-amino-B-hydroxynaphthalene-'i-sulphon'ic acid twice, a first time in a weak acid medium with a diazo-compound I and a second time in an alkaline medium with a diazo-compound II, to produce a dyestufi of the general type:

Diazo-compound I Diazo-compound II- the two diazo-compounds I and II being derived from an aromatic ortho-hydroxy-amine and at least one of them having a hydroxy group and a carboxyl group in ortho-position to one another, and treating the dyestufi thus obtained with an agent yielding a trivalent metal.

13. A process of preparing mordant polyazodyestuiTs and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-'l-sulphonic acid twice, a first time in a weak acid medium with a diazo-compound I and a second time in an alkaline medium with a diazo-compound II, to produce a dyestufi of the general type:

, 1|)iazo-compound I HSOs- NH,

Diem-compound II--- the two diam-compounds I and II being derived from an aromatic ortho-hydroxy-amine and at least one of them having a hydroxy group and a carboxyl group in ortho-position to one another, and treating the dyestuff thus obtained with a chromium yielding agent.

14. A process of preparing mordant polyazodyestuffs and water soluble metal compounds thereof, consisting in coupling 2-amino-5-hydroxynaphthalene-7-su1phonic acid twice, a first time in a weak acid medium with a diazo-compound I and a second time in an alkaline medium with a diazo-compound II, toproduce a dyestuif of the general type:

ll)iazo'compound I HSO3 NH:

Diazo-compound II the two diam-compounds I and II being derived from an aromatic ortho-hydroxy-amine and at least one of them having a hydroxy group and a carboxyl group in ortho-position to one another, and treating the dyestuff thus obtained with chromium acetate.

15. A process of preparing mordant polyazodyestuffs and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-'Z-sulphonic acid twice, a first time in a weak acid medium with a diazo-compound I and a second time in an alkaline medium with a diazo-compound II, to produce a dyestufi of the general type:

HSOa- NH:

Diazo-compound H- the two diazo-compounds I and II being derived from an aromatic ortho-hydroXy-amine and at least one of them having a hydroxy group and a carboxyl group in ortho-position to one another, and treating the dyestufi thus obtained with a bivalent and a trivalent metal yielding agent.

16. A process of preparing mordant disazo-dyestuffs and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-7-sulphonic acid twice, a first time in a weak acid medium with a diazotized orthoamino-salicylic-acidcompound and a second time in an alkaline medium with a diazotized ortho-amino-phenol compound, and treating the dyestufi thus obtained with a copper yielding agent.

17. A process of preparing a mordant disazodyestuif and a water soluble metal compound thereof, comprising coupling 2-amino-5-hydroxynaphthalene-'Z-sulphonic acid twice, a first time in a weak acid medium with diazotized orthoamino-para-sulphosalicylic acid and a second time in an alkaline medium with diazotized 1- amino-2-hydroxy5-chloro-3-su1phonic acid, and treating the dyestufi thus obtained with copper sulphate.

18. A process of preparing mordant disazo-dyestufis and water soluble metal compounds thereof, comprising coupling 2-amino-5-hydroxynaphthalene-'I-sulphonic acid twice, a first time in a weak acid medium with a diazotized orthoamino-salicylic acid compound and a second 'time in an alkaline medium with a diazotized ortho-aminophenol compound, and treating the dyestuff thus obtained with a chromium yielding agent.

19. A process of preparing a mordant disazodyestuff and a water soluble metal compound thereof, comprising coupling 2-amino-5-hydroxynaphthalene-'l-sulphonic acid twice, a first time in a weak acid medium with diazotized orthoamino-para-sulphosalicylic acid and a second time in an alkaline medium with diazotized 1- 'amino- 2 -hydroxy- -nitrobenzene- 3 -sulphonic acid and treating the dyestuif thus obtained with chromium acetate.

20. Water soluble metal compounds of polyazodyestuffs corresponding to the following general formula:

N=N-R1 HSOr- NH:

OH o

wherein the two aromatic radicals R1 and R2 bear formula:

1TI=N-R1 HSOa- NH:

wherein the two aromatic radicals R1 and R2 bear a hydroxy group in ortho-position to the azogroups and at least one of them has a carboxyl group in ortho-position to a hydroxy group, these dyestuffs containing chromium in complex combination.

23. The new water soluble cupriferous disazodyestuif, obtained by coupling 2-amino- 5-hydroxynaphthalene-l-sulphonic acid twice, a first time in a Weak acid medium with diazotized ortho-amino-para-sulphosalicylic acid and a second time in an alkaline medium with diazotized 1-amino-2-hydroxy- 5 -chloro- 3 -sulphonic acid and treating the dyestufi thus obtained with a copper yielding agent.

24. The new water soluble chromiferous disazodyestufi, obtained by coupling 2-amino-5-hy-' droxynaphthalene-7-sulphonic acid twice, a first time in a weak acid medium with diazotized ortho-amino-para-sulphosalicylic acid and a second time in an alkaline medium with diazotized 1-amino-2-hydroxy-5-nitrobenzene- 3 -sulphonic acid and treating the dyestufl thus obtained with a chromium yielding agent.

, MAX MI'TLLER.

ROGER RATTI. 

